This invention relates to the production of normally liquid, saturated hydrocarbons, useful in gasoline blending, by reacting isoparaffins with olefins in liquid phase in the presence of a substantially anhydrous crystalline aluminosilicate zeolite, and to means of preparing such zeolites.
This application contains claims copied from U.S. Pat. No. 3,549,557 (Cl. 252-455) to Anthony P. Bolton and Paul E. Pickert, which issued December 33, 1970, on application Ser. No. 740,049, filed June 26, 1968. Said claims have also been presented (by amendment filed on Dec. 20, 1971) in our patent application Ser. No. 716,190 (which was filed Mar. 26, 1968).
In the prosecution of Ser. No. 740,049, the following patents were cited: U.S. Pat. No. 3,251,902 to Garwood et al, Cl. 260-683.64 U.S. Pat. No. 3,397,137 to Pickert et al, Cl 252-455X.
In U.S. Pat. No. 3,549,557, a zeolite which contained exchanged cations of polyvalent metals was defined as containing its maximum OH exhibiting infrared absorption in the region of 3480 to 3670 cm.sup.-1, When "the thermally removable OH content of a given molecular sieve is fully developed (i.e., is at its maximum) . . . ". This maximum was further defined as being attained "when the zeolite has been heated to between 300.degree. C. and 400.degree. C.". This definition is used in the present application.
It was further stated that at least 40% of these OH can be thermally removed by heating the zeolite in the range off 550.degree. C. to 800.degree. C. For purposes of the present application, it is applicants' definition that this requirement for removal of at least 40% of these OH is met when the zeolite has lost 40 weight % of the "water" content at said maximum and that a zeolite which has been heated to 300.degree. C., or higher, (572.degree. F. contains no more than said maximum of these OH. Therefore, the requirement that a zeolite contain "less than about 60 percent of its maximum OH exhibiting infrared absorption in the region of 3480 to 3670 cm.sup.-1 is defined herein as requiring that the zeolite has "total water", as determined by weight, loss on ignition (LOI), that is no more than 60% of the "total water" which the zeolite had after heating for 60 minutes at 300.degree. C. In Table 4 hereof, (which is taken from our Ser. No. 716,190) the column headed "% max OH" is such a calculation made from the reported "total H.sub.2 O", obtained by ignition analysis.
Thus, Table 4 describes catalysts of the previously referred to chemical formulae and which, by definition, exhibit less than 40% (e.g. Run No. E-7) and less than 60% (Run No. E-9) of said maximum OH. These results are summarized below:
______________________________________ Run No. Temp. (.degree.C.) Total H.sub.2 O % Max OH ______________________________________ E-4 300 0.216 100 E-5 400 0.182 84 E-6 500 0.157 77 E-7 600 0.127 59 E-8 700 0.116 54 E-9 700 0.083 39 ______________________________________
A zeolite similar in preparation to E-7, except that it had been activated for 2 hours at 600.degree. C. (and an estimated LOI of about 2.5.+-.0.2%), was used as the catalyst in the alkylation run in Example XIII (hereinafter) which produced 128.5% of C.sub.5+ paraffin (based on olefin charged). Table 23 herein provides additional analytical data on this alkylation product.
A more precise correlation (or definition) of the maximum OH exhibiting infrared absorption in the region of 3480-3670 Cm.sup.-1 is that this maximum corresponds to the value at 300.degree. C. in the "H.sub.2 O for Ce" column of Table 4 herein. The requirement that a catalyst contain less than about 60 percent of said maximum is met when the "H.sub.2 O for Ce" has decreased by about 40% or more.
This correlation or definition can be seen in the following Table (taken from the Table 4 data):
______________________________________ Run No. Temp. (.degree.C.) H.sub.2 O for Ce % Max OH ______________________________________ E-4 300 0.136 100 E-5 400 0.102 75 E-6 500 0.075 55 E-7 600 0.046 34 E-8 700 0.037 27 E-9 700 0.007 5 ______________________________________